Clean Technology (청정기술)

The Korean Society of Clean Technology (한국청정기술학회)
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Dry reforming of Propane to Syngas over Ni-CeO2/γ-Al2O3 Catalysts in a Packed-bed Plasma Reactor

충전층 플라즈마 반응기에서 Ni-CeO2/γ-Al2O3 촉매를 이용한 프로페인-합성 가스 건식 개질

  • Sultana, Lamia (Department of Chemical and Biological Engineering, Jeju National University) ;
  • Rahman, Md. Shahinur (School of Physical, Environmental and Mathematical Sciences, the University of New South Wales (UNSW Sydney)) ;
  • Sudhakaran, M.S.P. (Department of Chemical and Biological Engineering, Jeju National University) ;
  • Hossain, Md. Mokter (Department of Chemical and Biological Engineering, Jeju National University) ;
  • Mok, Young Sun (Department of Chemical and Biological Engineering, Jeju National University)
  • Received : 2018.08.04
  • Accepted : 2018.11.13
  • Published : 2019.03.30
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Abstract

A dielectric barrier discharge (DBD) plasma reactor packed with $Ni-CeO_2/{\gamma}-Al_2O_3$ catalyst was used for the dry ($CO_2$) reforming of propane (DRP) to improve the production of syngas (a mixture of $H_2$ and CO) and the catalyst stability. The plasma-catalytic DRP was carried out with either thermally or plasma-reduced $Ni-CeO_2/{\gamma}-Al_2O_3$ catalyst at a $C_3H_8/CO_2$ ratio of 1/3 and a total feed gas flow rate of $300mL\;min^{-1}$. The catalytic activities associated with the DRP were evaluated in the range of $500{\sim}600^{\circ}C$. Following the calcination in ambient air, the ${\gamma}-Al_2O_3$ impregnated with the precursor solution ($Ni(NO_3)_2$ and $Ce(NO_3)_2$) was subjected to reduction in an $H_2/Ar$ atmosphere to prepare $Ni-CeO_2/{\gamma}-Al_2O_3$ catalyst. The characteristics of the catalysts were examined using X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectrometry (EDS), temperature programmed reduction ($H_2-TPR$), temperature programmed desorption ($H_2-TPD$, $CO_2-TPD$), temperature programmed oxidation (TPO), and Raman spectroscopy. The investigation revealed that the plasma-reduced $Ni-CeO_2/{\gamma}-Al_2O_3$ catalyst exhibited superior catalytic activity for the production of syngas, compared to the thermally reduced catalyst. Besides, the plasma-reduced $Ni-CeO_2/{\gamma}-Al_2O_3$ catalyst was found to show long-term catalytic stability with respect to coke resistance that is main concern regarding the DRP process.

프로페인($C_3H_8$)의 건식 개질($CO_2$ 개질)을 통한 합성 가스($H_2$와 CO 혼합물) 제조를 위해 $Ni-CeO_2/{\gamma}-Al_2O_3$ 촉매가 충진된 유전체 장벽 방전 플라즈마 반응기를 사용하였다. 열 또는 플라즈마에 의해 환원된 $Ni-CeO_2/{\gamma}-Al_2O_3$ 촉매를 사용하여 $C_3H_8/CO_2$ 비율 1/3, 총 유량 $300mL\;min^{-1}$에서 플라즈마-촉매 건식 개질을 수행하였다. 건식 개질에 대한 촉매 활성은 온도범위 $500{\sim}600^{\circ}C$에서 평가되었다. $Ni-CeO_2/{\gamma}-Al_2O_3$ 촉매 제조를 위해 전구물질 수용액(질산니켈, 질산세륨)으로 함침된 ${\gamma}-Al_2O_3$를 공기 분위기에서 소성시킨 후, $H_2/Ar$ 분위기에서 환원시켰다. 촉매 특성 조사에는 X-선 회절분석기(XRD), 투과전자현미경(TEM), 전계 방출 주사전자현미경(FE-SEM), 승온 탈착($H_2-TPD$, $CO_2-TPD$) 및 라만 분광기가 이용되었다. 열로 환원된 촉매와 비교하면 플라즈마 방전하에서 환원된 $Ni-CeO_2/{\gamma}-Al_2O_3$ 촉매가 개질 반응을 통한 합성 가스 생산에서 보다 우수한 촉매 활성을 나타내었다. 또한, 플라즈마로 환원된 $Ni-CeO_2/{\gamma}-Al_2O_3$가 개질 반응의 문제점인 탄소퇴적 관점에서 장기 촉매 안정성을 보여주었다.

Keywords

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Figure 1. Schematic of the plasma-assisted catalytic dry reforming reactor.

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Figure 2. TEM images of the thermally reduced (a and b) and plasma-reduced (c and d) catalysts at different magnifications.

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Figure 3. SEM images of (a) the thermally reduced and (b) plasma-reduced catalysts.

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Figure 5. XRD patterns of (a) bare γ-Al2O3, (b) calcined catalyst, (c) thermally reduced Ni-CeO2/γ-Al2O3, and (d) plasma-reduced Ni-CeO2/γ-Al2O3.

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Figure 6. H2-TPD curves of the Ni-CeO2/γ-Al2O3 catalysts.

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Figure 7. CO2-TPD curves of the Ni-CeO2/γ-Al2O3 catalysts.

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Figure 8. Conversions at different temperatures: (a) C3H8 and (b) CO2.

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Figure 9. Concentrations of (a) H2 and (b) CO obtained at different temperatures.

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Figure 10. SEM images of the catalysts after dry reforming reaction: (a) TRC, (b) TRC+Plasma, (c) PRC, and (d) PRC+Plasma.

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Figure 11. Raman spectra of the Ni-CeO2/γ-Al2O3 catalysts after dry reforming reaction: (a) TRC, (b) TRC+Plasma, (c) PRC, and (d) PRC+Plasma.

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Figure 4. (a) Elemental mapping image and (a*) EDS spectra of the thermally reduced catalyst, and (b) elemental mapping image and (b*) EDS spectra of the plasma-reduced catalyst catalyst.

Table 1. Number of desorbed H2 molecules determined by H2-TPD

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Table 2. Number of desorbed CO2 molecules determined by CO2-TPD

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Table 3. Experimental conditions for the dry reforming reaction

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Table 4. Amount of carbon deposition in wt%

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